Method and apparatus for hydrogenation and distillation



E. M. CLARK March 2l, 1933.

METHOD AND APPARATUS FOR HYDROGENATION AND DISTILLATION.

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METHOD AND APPARATUS FOR HYDROGENATION AND DISTILLATION Y Filed Jan. 26,1922's 2 sheets-sheet 2 n MM www QNNMJQ NN L QQ I NMR v@ Sb MWL www@ @NOD NU Patented Mar. 2l, 1933 EDGAR M. CLARK, OF GREEN'WICH,

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COMPANY METHOD AND APPARATUS FOR HYDBOGENATION AND DSTILLATIONApplication led January 26, 1928. Serial No. 249,584.

The present invention relates generally to the art of hydrogenatinghydrocarbonoils. More specifically, it comprises an improved process andapparatus for producing large 5 yields of valuable products from oilssuch as crude petroleum or reduced crude, with or without othercarbonaceous matter. The invention will be fully understood from thefollowing description and the drawings which illustrate preferredmethods and apparatus.

Fig. 1 is a semi-diagrammatic view in elevation of a continuous batteryof shell stills, in combination with high pressure hydrogenationequipment, and illustrates the flow of materials through the apparatus;and

Fig. 2 illustrates a modification in which pipe or coil stills aresubstituted for the shell stills.

Referring to Fig. 1 of the drawings, stills 1, 2, 3, 4, and 5 arearranged as a continuous battery and it is to be understood that eithera greater or lesser number of such stills may be used. These stills areof the ordinary shell type, and each is preferably fitted with 2J arectifying column 6, 7, 8, 9, and 10 respectively, of any suitabledesign. Bell-cap plate columns are perhaps most satisfactory. Eachcolumn is provided with a refiuxing ncoil 12, which also serves as ameans for "o preheating the oil which is fed by a line 11 to the coils12. Preheated oil is collected in a hot oil line 13 and the coils 12 arepreferably arranged so that each may be fed with a regulated quantity ofoil in accordance with the coolingdesired in each column. There is aby-pass line 14 connecting the cold oil line 11; with the hot oil line13. The total feed is collected in line 15.

Towers 6, 7, 8, 9, and 1-0 are litted with lo vapor lines 16, 17, 118,19, and 20, respectively, and each vapor line communicates withacondenser, not shown, so that a separate distillate may be obtained fromeach still. Oil is fed to tower 6 by line 21, as will J be describedbelow, and distillate is removed from the tower 6 by vapor line 16.yBottoms or unvaporized oil collects in still 1, which is heated bycombustion gas or otherwise. Steam may be injected into the still byspray 59 pipe 22, if desired. The unvaporized oil is fed to tower 7 by allow line 23 which may be provided with a pump, but it is preferable toinject a small quantity of steam into the line to induce the flow. Theoil iows to remaining stills in series, as will be understood, eachstill produc-ing a cut or fraction of oil. Residuum from still 5 iswithdrawn by line 24 and may be run to storage by line 24 or preferablycombined with the oil from line 15 and conducted to a high pressure pump25. l

Pump 25 forces the oil under high pressure through a pipe 25 and, ifdesired, to a heat exchanger 26, in which the oil temperature is raised,and then into line 27. Hydrogen or a gas containing hydrogen is fed byline 28, as will be described below, into line 27 through a mixer 29.The "mixer may be of any preferred design but it has been foundsatisfactory to feed the hydrogen into the oil through a perforated orporous plate so as to form a substantially homogeneous mixture,whichthen passes through pipe 30 into a coil 31, preferably heated bycombustion gases.

Coil 31 discharges into a line 32 carrying 75 the heated mixture of oiland hydrogen under high pressure into a plurality of highpressurereaction chambers or reactors for hydrogenation. Two reactors 33and 34 are shown, but the number may be varied. They are similar inconstruction and preferably consist of heavy metal shells designed towithstand heat, pressure, and the action of hydrogen. The shells arepreferably not heated externally but are heavily lagged against loss ofheat. They may be fitted with internal electrical heaters (not shown) ormay depend solely on heat carried by the oil and hydrogen from coil 31.

If desired, the temperature of the reactors 33 and 34 may be maintainedby circulating a part of the charge through a line 39 and suitablemeans, such as a surge pump 40, to the i'nlet of coil 31. Coil 31 may beeliminated and the heat supplied by the internal heaters mentioned, butI prefer to heat by coil 31, as described above. Means for stirring oragitating, such as the paddles 35, or other means for obtaining intimatemixing in the reactors may be used. Pipe 32 discharges through a 100branch pipe 32' and a spray head 36. Hot hydrogen-containing gas is fedby branch pipe 37 to a second spray head 38. Other methods ofintroducing the gas and oil may Y 5 be used, such as nozzles, and thelike.

. erably heated by heaters 48, 48', before entering the secondaryreactors in which it may be distributed and thoroughly mixed, as byspray pipes 49. However, the reactors may be heated internally, ifdesired. Catalytic masses are provided in reactors 45 forpromoting'reaction between the oil and hydrogen. Distillate oils,preferably preheated, may be added by lines 51, 51'.

Vapor passes from the chambers 45 by lines 52, 52', into the vapormanifold 43, which conducts the vapor to a heat-exchanger 53, in whichthe incoming hydrogencontaining gas is preheated, as will be described.The hot products may then iiow to a second exchanger 26, which is usedtofurther preheat the incoming oil, as stated above, or this exchangermay be by-passed through valved line 53'. The vapor, with anycondensates formed from it, iiows thence to a cooler 54. Pressurecontrol valves 52 and 52b are` installed in lines 52, 52', respectively.The cooled products then pass to a drum 55 for separation of gas fromliquid. The latter is continuously removed by line 56 and is conveyed bylines 57 and 58 into line 21 and thence to the tower 6 of still 1, aswas described above, or out of the system through pipe 57'. Pressurecontrol valves 55', 55", respectively, are provided in the inlet andoutlet lines connecting drum 555 Gas from drum 55 fiows by line 59 to apurifying tower 60, Where it is washed to remove impurities, such ashydrogen sulfid. A water solution of caustic soda or carbonate of sodamay be used and the liquid is preferably recirculated by line 61, pump62, and line 63. Gas may be vented, when required, through line 59'.Spent purifying solution may be withdrawn by line 64 and revivied ifdesired.

Gas from tower 60 passes preferably through line 65 to a tower 66 to bewashed with a suitable medium, such as petroleum oil, for removal ofmethane or other light hydrocarbons and any remaining hydrogen sulfid.Wash oil is forced into the top of tower 66 by pump 67 and line 68 andwithdrawn by line 69 to apparatus (not shown) for removing the dissolvedgas from the oil. The purified gas flows'from the top of tower 66 by aline 70 to a booster pump 71. Fresh gas may be added by line 72 and thehighly compressed mixture isl fed to the heat exchanger 53, as describedabove, by line 73, and thence by line 74 to a manifold 75.Hydrogen-containing gas is distributed in regulated quantities to pipes28, 37, 37 and 47, 47', as has been described, and through these pipes'respectively to mixer 29, primary reactors 33 and 34, and secondaryreactors 45.

Referring now to Fig. 2, it will be seen that the shellstills 1 to 5have been replaced by coil heaters 100 and 101, each provided with tworectifying columns 102 and 103 for heater 100, 104 and 105 for heater101. More than 2 heaters could obviously be used, but for illustrativepurposes, two only are shown. The crude oil is fed by pipe 106 and ispassed through the coils in towers 103, 102, 105 and 104 in the ordernamed. By-pass lines (not shown) are preferably provided so that thecooling effect in each tower may be suitably regulated. Hot oil fromcoil 12 in tower 104 then passes by line 106 to hydrogenation equipmentsimilar to that described in connection with Fig. 1, but shown in asomewhat simpler form, the gas purif ing system in particular beingomitted. n Fig. 2 only one primary reactor 33 and only one secondaryreactor 45 are shown, for simplicity, but two or more may be provided asin Fig. 1. The flow of materials through the hydrogenating equipmentneed not be traced again.

A line 107 conveys oil from heater 100 to tower 102. Vapor lines 108 and109 lead from towers 102 and 103, respectively. Bottoms or unvaporizedoil may be withdrawn from tower 103 by line 110, after stripping bysteam injected through line 111, if desired. Bottoms from tower 102 passto coil 101 through line 112 and pump 113. Towers 104 and 105 areprovided with vapor lines 114 and 115 respectively. Lines 116 and 117conduct unvaporized oil from these towers.

4A by-pass 116connects line 116 with line In operation of my improvedprocess with the equipment shown in Fig. 1, the preheated crudepetroleum or reduced crude is usually mixed with heavy residuum from thestills and the mixture is passed into the hydrogenation zone. The `oilin reactors 33 and 34, which may be used continuously, is held underpressure of 50 or 100 to 200 atmospheres or more (preferably about 200atmospheres) and at a temperature of about 7 50950 F. A catalyst,preferably finely pulverized metal oxids, may be suspended in the oil onstarting up the unit and may be maintained in the reactors or circulatedaround through pipe 39 and coil 31. A catalystsuch as 90% chromium oxidand 10% molybedenum oxid has been satisfactorily used. The amount ofcatalyst may be widely varied. When using the catalyst described, it isdesirable to have it present in amount about 1/3 by volume of the oil inthe reactor at any. one time. i

The hydrogen-containing gas is preferably substantially pure hydrogenand is usually forced into the reactors 33 and 34, at a rate of from10,000 to 15,000 cu. ft. per bbl. of oil fed. Most of the asphalticmaterials that may be in the oil appear to be converted into low-boilingdistillates. From (S0-80% of total sulphur is ordinarily converted intohydrogen sulfid. The equipment described is especially adapted forrunning high sulphur oils. In a copending application Serial No. 249,585filed January 26, 1928, a system designed for low sulphur oils isdescribed and claimed. i

Gases and vapors from primary reactors 33 and 34 may be conducted intothe secondary reactors 45. A The latter operatepreferably-at 80W-950o F.and under the pressure maintained in the reaction chambers, althoughpressure in the secondary reactors may be satisfactorily reduced as lowas 25 atmospheres. Catalytic materials, similar to those used inreactors 33 andv34, are preferably arranged on trays or otherwise tosecure C; good Contact with vapors.

It appears that the Aoil is hydrogenated mostly in liquid phase in theprimary reactors 33 and 34, while the reaction in the secondary reactors45 is doubtless mostly in the gas or vapor phase. Whatever the nature ofthe reaction, substantially increased yields of low-boiling products areobtained when the secondary reactors are used.

The temperature is raised in the secondary reactors 45 by forcing in asupply of highly heated hydrogen or hydrogen-containing gas throughlines 47, 47 and heaters 48, 48. The rate of flow of hydrogen may vary,but should ordinarily be about.30,000 cu. ft. per bbl. of gasolineformed. Distillate oils. heavier than gasoline, such as heavy naphtha,kerosene, gas oil and the like, or mixtures of these oils, may b'epassed into reactors 45 through lines 51, 51', either as liquid orvapor. Such distillates may be obtained from the various stills of thecontinuous battery, as will lbe discussed below. While it is oftenadvantageous to provide secondary reactors 45, the use of reactors 33and 34 alone, gives good results.

Vapor from reactors 45 and/or 33 and 34 is cooled in preheating theincoming crude oil and incoming hydrogen, in exchangers v26 and 53,respectively. Normally liquid products are condensed in coil 54 andseparated in drum 55l from gases, which may contain low boilinghydrocarbons, hydrogen suld, etc., with residual hydrogen. The gas ispurified in any satisfactory manner, such as hydrogenated residuum onlyreturned to the stills.

The condensed hydrogenated oil, preferably as hot `as may be withoutallowing any substantial quantity of gasoline to be carried off by thegas, is conveyed to the battery of stills where it lis separated intofractions,

y such as gasoline, naphtha, kerosene, gas oil,

and lubricating oils, which are removed from the stills in the ordernamed. Pressure is substantially atmospheric and temperature isprogressively increased from the first to the last still, as in anordinary crude battery. The first still will be at a temperature between350 F. and 470 F., or higher, depending on the boiling range ofdistillate desired, and

the. last still in tlie `series may be as highas 700 F. The same generalrange of temperatures may be maintained in the coil heaters 100, 101,Fig. 2. Distillation takes place chiefly in towers 102, 103, 104 and105. The method of operating the equipment shown in Fig. 2 will beobvious from the foregoing description. v

If preferred, only gasoline, kerosene, and gas oil may be removed andthelubricating fractions, as well as the heavy residue, may be recirculatedto the hydrogenation and cracking equipment.

The present method is applicable to all petroleum oils, whether crude,reduced crude,- or heavy refinery residues, or shale oil and the like,and is particularly applicable to oils which contain large quantities ofsulphur. Finely divided coal or similar carbonaceous material may becommingled with the oil to form a fluent mass for hydrogenation and/ordistillation. The invention is not limited by any theory of the reactionnor by any illustrative example of either apparatus or process. Variouschanges and alternative arrangements may be made within the scope of thefollowing-claims, in which it is desired to include all novelty inherentin the invention.4

l claim: y

1. `lfrocess for obtaining valuable products from hydrocarbon oil,comprising forcing a mixture of the oil and hydrogen under high pressurethrough a heating zone, discharging the heated mixture into a reactionzone, maintained at a temperature in excess of about 7 50 F. and under apressure above about atmospheres, withdrawing a mixture of gases andvapors substantially free Lzio drogenation stage.

of liquid therefrom, cooling the same under full pressure, separatingthe condensate from the uncondensed gases, expandin said separatedcondensateinto the rst o a series of distillation zones, distillingunder substantially atmospheric pressure,` removing distillates from thedistillation zones, and returning the undistilled residue to thereaction zone. u

2. Process of continuously hydrogenating oil, comprising maintaining asupply of hydrogenated oil, distilling products from the hydrogenatedoil in a series of distillation zones without hydrogenation, preheatingfeed oil by indirect heat exchange with vapors produced insaiddistillation zones, hydrogenating the preheated oil at a temperatureabove about 750 F. and under a pressure aboveabout 50 atmospheres,separating hydrogen therefrom, passing the hydrogenated oil to the firstdistillation zone for progressive ow through the series, and comminglingthe residual oil from a later distillation zone with the preheated oilpassing to the hy- 3. Continuous hydrogenation and distillationapparatus, comprising aV heating coil adapted to raise oil underpressurein excess of 50 atmospheres to a temperature at which it reactswith hydrogen, a reactor, means for passing the hot oil into thereactor, means for supplying hydrogen at high pressure and temperatureto the reactor for intimate admixture with the oil therein, meansforsegregating gases and normally liquid products from the reactor,means forexpanding said liquid products to low pressure, means 'fordistilling lower boiling fractions from said liquid products undersubstantially atmospheric pressure, and means for contlnuouslyreturning, residual liquid products with hydrogen to the heating coiland thence tothe reactor.

4. Apparatus according to claim 3, in which means are provided forpurifying the gases under high pressure therefor returningY them to thereactor.

. 5. Hydrogenation and distillation apparatus, comprising means formixing oil with. hydrogen, means for heating said mixture under pressurein excess of 100 atmospheres, a primary reactor into which said heatedmixture may be discharged, a secondary reactor, means for passing vaporsfrom the primary reactor to the secondary reactor, means for supplyingadditional hot hydrogen to said secondary reactor, means for condensingnormally liquid products from the 'vapors from said secondary reactorand means for separating said liquid products from uncondensed gaseswithout substantial reductionv in pressure, means for expanding saidseparated liquid products into the first of ".a

series of distillation zones, and means :for distilling andfractionating said liquid products under atmospheric pressure.

6. Process for obtaining valuable products from a fluent carbonaceous.material which comprises heating the material inthe presence ofhydrogen at a pressure not substantially less than 50 atmospheres,withdrawing a mixture of` gases and vapors substantially free of liquid,cooling the same without any substantial reduction in pressure,separating the condensate from uncondensed gases, continuously expandingthe condensate into the first of a series of distillation zones anddistilling under a materially Lower pressure.

7 Process for obtaining valuable products 'fromme hydrocarbon oil, whichcomprises heating the oil inthe presence .of hydrogen at a pressure notsubstantially less than 100 atmospheres, withdrawing a mixture of gasesand vapors substantially free of liquid, cooling the same undersubstantially the same pressure, separating the condensate fromuncondensed gases, continuously expanding the condensate into the firstof a series of distillation zones and distilling under a materiallylower pressure.

8. Process according to claim 7 in which the undistilled residue fromone or more of the distillation zones is returned to the hydrogenationstep. l

9. Process for obtaining valuable distillate oils from heavy hydrocarbonoil, comprising heating the oil in the presence of hydrogen at apressure not substantially'less than 100 atmospheres, withdrawing amixture of gases and vapors substantially free of liquid, condensing outnormally liquid products from the gases and vapors, continuouslyexpanding the liquid products into a distillation zone, distillingwithout hydrogen, collecting distillate oils from said zone, andreturning the undistilled residue to the hydrogenation step.

10. Process for obtaining valuable distillates from petroleum oil,comprising suspending a catalytic material in the oil, maintaining abody of the suspension under a pressure not substantially less than 100Aatmospheres, and temperature in excess of 750 F., forcing a gas rich infree hydrogen mospheres, and temperature in excess of 750 F., forcing agas rich in free hydrogen into the suspension, removing gases and vaporsfrom said body of oil and subjecting them before being cooled tohydrogenation in vapor phase in a second reaction zone, withdrawing amixture of gases and vapors substantially free of liquid -from saidsecond zone, condensing normally liquid products from the gases andvapors, releasing pressure on said liquidproducts, distilling the liquidproducts under substantially atmospheric pressure in a seri'es ofdistillation zones, collecting distillates from the distillation zones,and returning the undistilled residue to the body of oil under highpressure.

12. Process according to claim 11 in which the vapors evolved from thebody of oil are passed through the secondary reaction zone with anadditional quantity of gas rich in free hydrogen.

13. Process according to claim 11 in which the secondary reaction zoneis maintained at a temperature in excess of 800 F. and under a pressureabove 25 atmospheres.

EDGAR M. CLARK.

